Patent GB-313865-A (GB)
Title: Manufacture of new azo-dyestuffs
IPC: C09B29/20
Filed: 1928-03-12
Abstract: 313,865. Imray, O. Y., (I. G. Farbenindustrie Akt.-Ges.). March 12, 1928. Azo dyes are made by combining a 4-diazo-N- nitrosodiarylamine not containing a sulphonic or carboxylic group with an arylide of 2 : 3-oxynaphthoic acid. The arylides may be derived from aniline, toluidines, o- and p-aminoethylbenzenes, alkyl-, aralkyl- and aryl-ethers of aminophenols, amino-phenyl-ketones, sulphones and -sulphamines and their halogen substitution products, arylenediamines, diaminodiaryls and their derivatives and diamines in which two aryl residues are united by a group such as -CH2-, - CO- or -NH-CO-NH-. Arylides prepared from substituted 2 : 3-oxynaphthoic acids (except sulphonic and carboxylic derivatives) are also specified. The nitroso group in the dyestuff may he removed bv means of saponifying agents advnntageously with addition of a reducing agent. The diazo-nitroso-diphenylamine compounds, which form stable solutions, are obtained by the action oi an alkali nitrite (2 mols.) on a 4-aminodiphenylamine (1 mol.). In an example, 4<1>-methoxy-N- nitrosodiphenylamine - 4 - diazonium chloride is coupled with the anilide of 2 : 3-oxynaphthoic acid and the nitroso group removed with sodium sulphide and soap solution. As first components the diazo-N-nitroso compound of the following are also specified : 4-amino-, 4-amino-21 (or 3<1> or 4<1>)- methyl-, 4-amino-21- (or 41)-methoxy-, 4-amino-2<1>- (or 4<1>)-ethoxy-, 4-amino-2<1>- (or 4')-phenoxy-, 4- amino-2<1>- (or 3<1> or 4<1>)-chloro-, 4-amino-3-methyl- 4<1>-methoxy-, 4-amino-3<1>-methyl-6<1>-methoxy-, 4- amino-2<1>-methyl-4<1>- (or 5')-chloro-, 4-amino-3'- methyl-6<1>-chloro, 4-amino-4<1>-methyl-3<1>-chloro, 4- amino-2<1>-methoxy-4<1>-chloro-, 4-amino-3-methoxy- 6: 2<1> - dimethyl - 4<1>-chloro, 4-amino-3<1>- : 4'-di. chloro-, 4-amino-3 : 2<1>-dimethoxy-, 4-amino-3 : 2'- dimethyl and 4-amino-3 : 2<1>-diehlorodiphenylamine and 4-aminophenyl-#-naphthylamine. As second components the following are also specified : o-, m and p-chloranilide, o-, m- and p-phenetidide, a- and /3-naphthylamide, 4- and 5-chloro-2-anisidide, dianisidide, 2-phenoxy-1-anilide, 4-benzyloxy-1-anilide, 2 : 5-dimethoxy-1-anilide, 3-methoxy-2-naphthylamide, 2-, 3- and 4-toluidide, 2- and 4-etlyl-1-anilide, 2-ethyl-5-chloranilide, 3- n;ti,anilide, 5-chloro-2-toluidide and 2-, 3- and 4- anisidide of 2 : 3-oxynaphthoic acid and di- (2" : 3<11>-oxynaphthoyl) - 4 : 4<1> - diamino - 2 : 21 : 5 : 5'- tetrachlorodiphenylurea, 2 : 3 - oxy - naphthoyl-3- aminoacetophenone, 2 : 3-oxy-naphthoyl-3-amino- 4-methoxybenzene sulphonic acid dimethylamide, 2 : 3 - oxynapthoyl-2-aminotolyl-4-ethylsulphone, di - (2<11> : 3<11> - oxynaphthoyl) - 4 : 4<1> - diamino - 2 : 2<1> - dimethyldiphenylmethane, di - (2<11> : 3<11>-oxynaphthoyl)-4 : 4<1>-diaminobenzophenone and the anilide, 5-chlolo-2-anisidide, 2-anisidide and 1- naphthylamide of 6-bromo-2 : 3-oxynaphthoic acid. Specifications 6379/12, and 17279/13, [Class 15 (ii), Dyeing, Processes &c. for], are referred to. Diphenylamine derivatives.-The above diphenylamine compounds may generally be prepared by condensing the appropriate aromatic amino compounds bearing the corresponding substituents with p-nitrochlorobenzene-o-sulphonic acid and its coresponding nuclear substitution products, reducing the nitro group in the condensation product and eliminating the sulphonic group by hydrolysis. 4-Amino - 3 - methoxy-6: 2<1>-dimethyl-4<1>-chlorodiphenylamine is made by methylating the azo compound 5-chloro-2-toluidine # p-cresol and transforming the product according to Jakobson's method. 4-Amino-3-methyl-4<1>-methoxydiphenylamine is similarly prepared from the methylated azo compound o-toluidine # phenol. 4-Amino-3 : 2<1>-dimethoxydiphenylamine is made by treating o-nitrosoanisole with sulphuric acid and reducing the 4-nitroso-2: 3<1>-dimethoxydiphenylhydroxylamine thus formed. 4-Amino-3 : 2<1>-dichlorodiphenylamine may be similarly prepared from o-chloronitrosobenzene. 2 : 3-Hydroxynaphthoyl derivatives may be made from 2 : 3-oxynaphthoic acid or the appropriate substitution product thereof and the corresponding amine by the process of Specification 13237/13. 4 : 4<1> - Diamino-2 : 2<1> : 5 : 5<1>-tetrachlorodiyhenylurea is made from 2 : 5-dichloro-4-nitraniline and phosgene and reducing. 4-Chloro-2-amino-1-ethylbenzene is made by replacing the amino group in 2-nitro-4-amino-1- ethylbenzene by chlorine and reducing the 4- chloro-2-nitro-1-ethylbenzene thus obtained.